Aromatic methyleneamino compounds and process of preparing the same



Patented Nov. 18, 1930 the formation of asymmetric MYBTI KAHN, or coLoe in'wmnEmvr sorrnrss, on LEvnnKussN-oN-TH -nmnri,

AND LUDWIG ZEI-I,

ER-AL ANILINE wonirsano, on NEW YORK, N.

No Drawing.

The present inventionv concerns the manufacture of benzyl condensation products of the aromatic series bythe interactionof a halogenmethylderivative of an hydroxycompound of the aromatic series with an arcmatic amine at ordinary temperature.

It is known from U. S. Letters Patent 67.55% and British specification No. 265,203 that, when formaldehyde and hydrochloric acid act'on hydroxy-carboxylic acids chloromethyl derivatives of the same are produced, which on heating further react-with primary, secondary and tertiary amines with diphenylmethane derivatives. a Inaccordance with this invention aromatic amines and their derivatives also enter into reaction with halogenmethyl compoundsof the aromatic series in quite a difierent man-" ner, viz., the halogenmethyl compounds "attach themselves to the nltrogen'atom, when the reaction is earned out at room temperature, whereas at higher temperatures, as for example at the temperatureof the water bath,

they enter into the nucleus as already stated. Thepresent inveiition'theretore, only concerns the first case, whereby compounds of the general type ooon are obtained, i. c., ben zyl derivatives of the aromatic amines, in which R signifies hydrogen or an alkyl or aryl residue, when prlmary and secondary bases are used.' In" the case i where tertiary amines, such as'pyridine, are

sult.

The new products are generally whitish /I r O 7 R1 R stands fora benzene or naphthalene radicle, R stands for hydrogen or asubstituent employed, quaternary ammonium salts reor wrnsnonr-on-rnn-nmnn, GERM NY,- assreuoas'ro G N 17;, A conromirronor D LAWARE Application filed June 23, 1927,,Seria1 no. 201,017. and in Germany f ugust 1e, 1e26,

ARoiirATIo mnrrrynnnnemmo oorarounns Ann rnoonss or rnnrnnme the sway substituen't and y hydrogen or thecarboxylic group.

ner into p chloromethyl-salicylic acid, by means of formaldehyde and hydrochloric acid Which is filtered and washed with ice water. Thereupon l6parts by 'weight of m-sulphanilic acidare dissolved in' cold so- Ewamplell-els parts by eight of sali i 'cylic 'acidare converted in the known man dium'carbonate solutiontand the cl loromethylsalicylic acid obtained above is introduced at room temperatureintothis solution, wh ch is maintained weakly alkaline with sodlum carbonate. After Q l-hOursthe Whole acidified with hydrochloric acid and the precipitated product filtered, washed and dried. It formsa wh'itepowder, which Z iseas'ily soluble inyalkalies and cannotbe diazotized; The product'has the formula sotinic. acid are transformed as described above l into the chloromethyl-o-cresotinic acid and this is stirred in solution weakly.

alkaline with. sodium carbonate with 24 parts by weight of 2.8-aminonaphthol-6 sul phonicacid atroom temperature. After'a few hours, the solution ceases to takeup nitrite. By acidification with hydrochloric acid the condensation product i OH O Ha Hogs ,\COVO;H\ is precipitated, it filtered, washed and dried. *Thenew acid is a yellowish crystalline powder, insoluble in acids,but easily soluble in alkalies and couples with diazo compounds with the production of dyestuffs.

Ewamplerlgwipartsby weight ofmonomethylaniline are suspended in 2000/parts j of waterwhilstvigorously stirring and efficiently cooling- The chloromethyl -deriva- I tive obtained according-to the customary I process from 135 parts by weight of o-cresotinic acid is then stirred in. After continuing the stirring for some two hours at room temperature, sodium carbonate is added until weak alkaline reaction prevails, the whole being thus dissolved. After further stirring for several hours, the excess of the base is removed by steamdistillation, when the remaining residue is precipitated with aceticacid. The new product is filtered,

washed anddried and has the following constitutlonz I (IJHIs V e ooon Emam JZe'4.The crude paste of chloromethylcresotinic acid, obtained from 150 parts by weight of cresotinic acid is washed with a little ice water and thus freed from the bulk of the adhering hydrochloric acid. It is then introduced at 010 G. into 500 parts by weight of pyridine whilst stirring. Soon after the whole amount has been added, solution occurs After several hours stirring, some of the reaction product separates from the solution, when hydrochloric acid 1s introduced until Congo acid reaction becomes noticeable. A thick magma of needles is thus produced, which is filtered and recrystallized from water. In this mannerbeautitul long needles of the pyridine compound Y i V are obtained, which melt at 204-206 C. The

new compound is soluble in alkali carbonates with development of carbonic acid, a colourless solution resulting, from which after short standing a compound separates, presumably the betain like anhydride. The pyridine compound and the betain form a yellow solution with caustic soda lye, which decomposes on heating with decolouration and splitting oil of pyridine.

We claim V 1. The process for the manufacture of condensation products of the aromatic series co1nprising the interaction or a halogenmethyl derivative of an hydroxycompound'of the aromatic series with an aromatic. amine at ordinary temperature.

:2. The new products being condensation products of the aromatic series, being whitish powders soluble in dilute alkalies produclng azo dyes with diazocompounds and having most probably the following general formula:

.1: L Ray-011F001: R1

It stands for a benzene -or naphthalene nucleus which may contain further substituents, R stands forhydrogen, alkyl or aryl. as means hydrogen or a substitutent and y hydrogen or the carboxylic group.

The new condensation product obtainazo dyes with diazocompounds and most probably the following general formula able from chloromethyl-ortho-cresotinic acid and Q-amino-8-naphthol-6-sulfonic acid having most probably the formula:

no3s oooH and being a yellowish crystalline powder insoluble in acids but easily soluble in alkalines and coupling with diazocompounds with the production of dyestuffs.

l. Th1 new products being condensation products of the aromatic series, being whitish powders soluble in dilute alkalies producing having 

